Materials for treatment of hydrocarbons



Patented Nov. 22, 1938 UNITED STATES MATERIALS FOR TREATMENT, OF HYDRO- CARBONS Edward F. Quirke, Brooklyn, N. Y.

No Drawing. Application March 27, 1937,

Serial No. 133,383

8 Claims. (CI. 44-43) This invention relates to improvements in materials for the treatment of hydrocarbons, and more particularly to such material for treatment of hydrocarbons used as fuel oil.

Considerable difficulty has been experienced in connection with the use of fuel oils by the presence of objectionable precipitate and in the formation of carbon scale. The objectionable precipitate is generally referred to as sludge, and comprises both the solid matters which precipitate, such as separated carbon, asphaltum or other relatively dense substances, as well as a proportion of water present in the tank from various causes, such as condensation, leakage and otherwise.

Fuel oil for heating purposes has been and is at present used either directly to the burner from the tank where the viscosity of the oil permits or is used by first passing it through apre-heater to render the oil less viscous and to permit of a more complete combustion of the oil. In the latter case, in due course, a deposit of carbon or asphalt is formed or baked on to the tubing of the heater. Thiscarbon or asphalt will have varying densities or hardness of structure or formation. This carbon has a high insulating quality and retards the proper heat transfer to the oil as it flows through the tubes of the .heater, but also gradually reduces the flow area of the pre-heater tubes.

More specifically, I would em asize that fuel oils of all gravities, or viscosities, carry a certain percentage of carbon, asphaltum, gum and resinousmatter in suspension ,and also havepresent a small percentage of water, particularly in the heavy oils ranging -from.- 81to 20 gravity Beaum. .The percentage of carbon in the oils will vary according to the refinery practice to which the oil is subjected prior to delivery to the customer. Also, the percentage of carbon will vary according to whether the oil is of asphaltic or paraffine base, or a combination of both and according to the field or source of supply from which the crude oil emanates. Oils from various fields will vary in character and may be consequently more or less waxy, may contain high or low percentages.

of volatile matter and will have in suspension varying amounts of water. Oils of. high gravity and of high volatility, after refining, will contain more or less sediment of a gummy, waxy and/or,

and form the objectionable sludge of a. heavy viscous nature which entraps more or less water as a result of'settling of the water arrivingwith the oil and condensation caused by atmospheric changes known generally as tank sweating.

As mentioned above, the fuel oils generally used with fuel burners contain a precipitate which ultimatelysettles in general practice within the storage tank of the user.

er or to the burner will cause ace'rtainamount of this heavy sediment to come through the oil suction line. Obviously this sediment Will increase the amount of carbon within the heater and will tend to hasten the formation of carbon on the heater tubing. The sediment, likewise, tends to collect in and clog the strainersof the oil piping equipment and/or system, reducing the flow of oil and interfering with the constant, even or perfect operation of the burner. It also causes undesirable carbon formation on the burner. In addition, the combustion with an'excess amount of carbon or solid matter induces a smoking stack, increases oil consumption and in general causes the burner operation to be less effective or efiicient. An object of the invention may there fore be stated as providing a material for use directly in the storage tank for eliminating detrimental efiect of the presence of precipitates or sludge in the oil) A variety of compounds are now on the market intended to have a beneficial effect upon the oil in the storage tank, but which actually fail to accomplish the result desired, and in some instances are more detrimental than helpful. It is to be emphasized that an essential of the composition to be used is that it shall not absorb water or moisture from the atmosphere and lose the property of breaking up or destroying the carbon sediment or sludge. The material must have the beneficial eifect of breaking up the carbon and enable the resultant atomic carbon and water carried in suspension to travel through the piping and burner freely with the oil, and the material must, in addition be effective to remove the carbon from the heater and burner as well as from the piping lines. Furthermore it is not desirable to use any chemicals or employ them in a composition which has a metallic base or nature such as oleates, stearates, and linoleates of metals such as aluminum, zinc and lead, as they tend to cling to, adhere and bake on the heater tubing, and

cause a condition which it is the purpose of the present invention to eliminate and/or prevent.

Furthermore, materials of like nature which will The oil pump by which the oil is drawn from the tank to the heatrise to the top of the oil or require special stirring, mixing or constant agitation, are not to be employed in a material i'i'aving the character and advantages of the'present invention. It may accordingly be said that objects of the invention are to provide a stable material of non-acid character, a material excluding metallic base or nature and a material of proper-specific gravity, and a material which in any event will function within the tank, piping system, heater and burner at the temperatures existent therein, and a material which is stable in bulk under ordinary conditions, which will keep for a long period of time, which will not absorb water, and of appropriate specific gravity with respect to the oil in which used.

Further objects of the invention are to provide a composition effective on a variety of different oils; to obtain a breaking or throwing up of the sludge sediment and cause it to pass through the burner at atomic carbon; and to provide a material for reducing the viscosity of the oil. Another object of the invention is the provision of a composition for the prevention of sludge formation in the tank by keeping the carbon in the oil in suspension and not allowing it to settle, and preventing the formation of carbon on heaters and burners when applied to the oil continuously. the quantities to be of a varying amount depending upon the viscosity, gravity and constituency of the oil.

As hereinbefore stated, a fuel oil system will accumulate sludge and water, sediments or emulsions in the tank. The piping lines will accumulate a sediment reducing the flow area, and carbon formations will appear on the heaters and burners. Hard carbon formations can appear in the combustion chambers of boilers or furnaces. The present invention is directed to providing a compound to eliminate this condition, or to clean the system, said compound comprising a hydrocarbon, a caustic and a phosphate with the use of a borax, depending upon the mode or use of the compound to meet any given condition, resulting from the use of fuel oil, which may be found.

The hydrocarbons are the most essential agents in breaking or throwing up the carbon sludge or sediment formations in the tank. These hydrocarbons can be of the so called hydrocarbon family such as napthalene, anthracene, phenanthrene and similar articles.

The addition of the borax and phosphate to the compound as a whole. according to this invention, in varying quantities as the characteristics of the oil and the condition of the heater warrant. are for the purpose of breaking up any hard carbon formations on the heater tubing and on the burners into minute particles' so as to be passed through the orifices of the burner and be consumed in the fire-box. The compound will reduce the viscosity of oil. 1

The alkalies or caustics are caustic soda. caustic potash and lime. Such compounds, preferably caustic soda, cut and dissolve the Waxes, gums and/or resins in the oil and prevent the formation, or accumulation, of such undesirable accretions on the sides and bottoms of tanks and in piping systems which induces carbon or asphaltic accumulation. In addition, the use of caustic sodas, or caustic potash, or lime, or a composition of all three, causes a heat generation in a tank containing an accumulation of sludge and water whereby the napthalene, or other hydrocarbons are dissolved more completely and causes a permeation of the sludge or oilwith the compound of this invention as a whole in order to obtain the desired results. The proportions of the formulas when including the caustic may be varied as to percentages, and the following formulas are merely illustrative of a number of suitable compositions embodying the present invention.

Example No. 1

Per cent Napthalene Caustic soda 30 Trisodium phosphate 7' Borax 3 Example No. 2

Per cent Napthalene '75 Caustic soda 15 Trisodium phosphate 6-7 Borax -l 4-3 Example No.3

Per cent Anthracene 3O Napthalene 30 Caustic soda 15 Caustic potash 15 Lime 4 Trisodium phosphate 4 Example N0. 4

Per cent Napthalene '75 Caustic soda 18 Trisodium phosphate 7 Example N0. 5

Per cent Caustic soda 20 Phenanthrene 40 Napthalene 30 Trisodium phosphate 10 The formula may be varied as to percentage and ingredients as mentioned, in order to apply to any character of oil or condition of carbon, sediment, or sludge, formation in tank, carbon on heaters and burners, as well as to lower the viscosity of oil.

In preparing the compound certain of the constituents are ground, mixed and aerated. The resultant is then mixed with certain other chemicals, and ground again so as to form a complete compound.

The especial characteristics of the foregoing formulas are that there is no pitting, erosion or corroding of metallic parts when mixed with oil or used to break up carbon sediment, sludge, or emulsion in tanks, or removing carbon from heaters.

Repeated tests over a long period of time have shown that such formulas retain their strength and are effective under all conditions of climate and temperature.

Experience and practical application has demonstrated that the compound as set out under the various examples reduces the viscosity of oils, or thins out oil in the storage tank, particularly in the range of gravities from 8 to 20. ,It would appear that this is accomplished in that, by reason of water inherently present in fuel oils, or the inclusion of water through the sweating of the tank or by leakage, or other means, the

caustic develops a heat which causes the naphthalene to dissolve and attack the oil film surrounding the solids or carbon matter always present in fuel; causing a separation of oil from the carbon or asphalt atom and a breakup of the carbon or asphalt constituents, so as to produce a thinner oil fluid. By reason of the water present in the 'oil, as just described, the trisodium phosphate is likewise dissolved. When the oil so treated with the compound passes through the piping and the tubing of the heaters, it has been found that it dislodges the tarry, asphalt or soft carbon formations on the heaters and piping and also the trisodium phosphate breaks down what is known as the hard carbon structure which may have baked on the tubes of the heater. It also breaks down the hard carbon formations on the burners.

Repeated tests and practical applications over a period of time have alsodefinitely proven that such a compound has prevented the formation of sludge and water emulsions in the tank. It has prevented carbon formations on the tubes of the heaters. It has prevented carbon formations on the burners. It has been found that through a breaking; down of the viscosity of the oil and by keeping the entire system free from sludge and carbon formations that the oil leaves the burner in a finer state of atomization so that there is a more complete combustion of the B. t. u. value of the oil and that certain economies in oil consumption are obtained.

By keeping the heater carbon-free, when the oil comes in contact with the bare hot metal of the tubes of the heater, there is a cracking process which also permits "heat transfer" that results in the oil being more finely liquefied than if a mere nominal heat transfer had been applied. That is to say, that by reason of the element of napthalene and trisodium phosphatethe constituency of the oil is broken up and by prevention of carbon formation on the tubes of the heaters theoii is further broken up by a heat process that it produces the results set forth.

In most oils whether of high or low gravity, there is inherently present a certain amount of acid as the result of refining operations. Practical itests and'usage over a periodof time demonstrate that the compound of my invention, neutralizes the acid condition in the oil and prevents pitting and eroding of the tanks. Examination of the interior of tanks over a period of .time has proven this allegation to be justifled.

Examples of use maybe given as preferablyintroducing one pound of compound to 400 to 600 gallons of sludge, carbon sediment, etc., of the heavy oils, and one pound of compound to 500 to 1000 gallons where oils are from 20 to 40 gravity Baum. Use may be on the basis of one pound of compound to 800 to 1000 gallons of oils of low gravity where it is desired to reduce viscosity and prevent sludge and carbon formation in tubes and heaters; or the same quantity on the basis of 1000 to 1500 gallons of oils of high gravity. The exact composition and the use of any given'formula will depend upon the condition to be met. While agitation of the oil or emulsion is desirable it is not essential with my compound as practical operating tests have demonstrated that permeation of the oil, or the sludge, is accomplished and the treated oil coursing through the tubing of the heaters breaks down and dislodges the carbon therefrom. v

I claim:

1. A composition for treating fuel oil of the. type normally tending to deposit substantial quan-' tities of sludge in storage tanks and forming objectionable carbon incrustations upon pre-heating depositions in use, comprising as a major portion of the composition a polycyclic hydrocarbon together with minor proportions of a caustic al.- kali'ingredient and a water soluble phosphate, and a small amount of a water soluble borate functioning to assist in removing or preventing said incrustations.

2. A composition for treating fuel oil of the type normally tending to deposit substantial quantities of sludge in storage tanks and forming objectionable carbon incrustations upon pre-heating apparatus and oil burners, and to prevent such depositions in use, comprising as a major portion of the composition a polycyclic hydrocarbon together with minor proportions of a caustic alkali ingredient and an alkali phosphate, and a small amount of an alkali borate functioning to.

assist in removing or preventing said incrustations.

3. A composition for treating fuel oil of the type normally tending to deposit substantial quantities of sludge in storage tanks and forming objectionable carbon incrustations upon preheating apparatus and oil burners, and to prevent' such depositions in use, comprising asa major portion of the composition a hydrocarbon selected from the group consisting of naphthalene, anthracene and phenanthrene, together with minor proportions of a causticalkali ingredient and a water soluble phosphate, and a small amount of a water soluble borate functioning to assist in removing or preventing said incrustations.

4. A composition for treating fuel oil of the type normally tending to deposit substantial quantities of sludge in storage'tanks and forming objectionable carbon incrustations upon pre-heat- ,ing apparatus and oil burners, and to prevent such depositions in use, comprising as a major portion of the composition a polycyclic hydrocarbon together with minor proportions of caustic soda and an alkali phosphate, and a small amount of an alkali borate functioning to assist in removing or preventing the formation of hard carbon onthe heater tubes.

6. A composition for treating fuel oil of'the type normally tending to deposit substantial quantities of sludge in storage tanks and forming objectionable carbon incrustations upon preheating apparatus and oil'bumers, and to prevent such depositions in use, comprising a hydrocarbon selected from the group consisting of naphthalene, anthracene and phenanthrene, together with minor proportions of a caustic alkali ingredient, an alkaliphosphate, and a small amount of an alkali borate functioning to asist )in removing or preventing said incrustations.

7 Acomposition for treating fuel oil containing a sludge component having a small percentage of water present, said composition comprising as a major portion of the composition a polycyclic.

hydrocarbon'together with minor proportions of 4i aw/e7 quantities of sludge in storage tanks and forming objectionable carbon incrustations upon preheating apparatus and oil burners which corrode the same or clog or react therewith, consisting of a major portion of a polycyclic hydrocarbon together with lesser proportions of a caustlcalkali ingredient and an alkali phosphate.

F. QUIRKE. 

